CN106319269B - A kind of Emission in Cubic Ca3Si alloys and preparation method thereof - Google Patents
A kind of Emission in Cubic Ca3Si alloys and preparation method thereof Download PDFInfo
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- CN106319269B CN106319269B CN201610935975.2A CN201610935975A CN106319269B CN 106319269 B CN106319269 B CN 106319269B CN 201610935975 A CN201610935975 A CN 201610935975A CN 106319269 B CN106319269 B CN 106319269B
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- 239000000956 alloy Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 229910045601 alloy Inorganic materials 0.000 title abstract description 9
- 239000010935 stainless steel Substances 0.000 claims abstract description 22
- 229910001220 stainless steel Inorganic materials 0.000 claims abstract description 22
- 239000000843 powder Substances 0.000 claims abstract description 21
- 229910000676 Si alloy Inorganic materials 0.000 claims abstract description 19
- 239000000203 mixture Substances 0.000 claims abstract description 18
- 238000005245 sintering Methods 0.000 claims abstract description 17
- 238000000498 ball milling Methods 0.000 claims abstract description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000001301 oxygen Substances 0.000 claims abstract description 8
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 8
- 239000011863 silicon-based powder Substances 0.000 claims abstract description 8
- 239000007789 gas Substances 0.000 claims abstract description 7
- 239000011812 mixed powder Substances 0.000 claims abstract description 6
- 230000001681 protective effect Effects 0.000 claims abstract description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
- 238000004140 cleaning Methods 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 8
- 229910052710 silicon Inorganic materials 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 238000010792 warming Methods 0.000 claims description 7
- 229910052791 calcium Inorganic materials 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 238000005054 agglomeration Methods 0.000 claims description 2
- 230000002776 aggregation Effects 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 8
- 239000011575 calcium Substances 0.000 description 35
- 125000004429 atom Chemical group 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 6
- 229910014458 Ca-Si Inorganic materials 0.000 description 5
- 229910004709 CaSi Inorganic materials 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 229910004706 CaSi2 Inorganic materials 0.000 description 3
- 238000002604 ultrasonography Methods 0.000 description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- 229910014526 Ca2Si Inorganic materials 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 229910021332 silicide Inorganic materials 0.000 description 2
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 230000005619 thermoelectricity Effects 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000009646 cryomilling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000002887 superconductor Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
- B22F3/1003—Use of special medium during sintering, e.g. sintering aid
- B22F3/1007—Atmosphere
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
- B22F3/105—Sintering only by using electric current other than for infrared radiant energy, laser radiation or plasma ; by ultrasonic bonding
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C24/00—Alloys based on an alkali or an alkaline earth metal
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
- B22F2009/041—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by mechanical alloying, e.g. blending, milling
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2999/00—Aspects linked to processes or compositions used in powder metallurgy
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- Engineering & Computer Science (AREA)
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- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
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- Metallurgy (AREA)
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Abstract
The invention discloses a kind of Emission in Cubic Ca3Si alloys and preparation method thereof, comprise the following steps：（1）Ca powder and Si powder are well mixed under Ar protective atmospheres in proportion, obtain mixture；（2）By the mixture, in Ar gas shielded atmosphere transfers ball grinder, by ball grinder good seal, oxygen is avoided to enter；（3）By step（2）In ready ball grinder, be put into ball mill and ball milling carried out with certain rotating speed, powder is fully reacted, obtain uniform mixed powder；（4）By step（3）In obtain uniform mixed powder and take out, in the stainless steel mould of specification needed for loading, carry out vacuum-sintering tabletting by the way of vacuum plasma sintering, produce Emission in Cubic Ca3Si sheets or bulk alloy material.The present invention has the advantages such as technique is simple, operation is easy, cost is low, the Emission in Cubic Ca of gained3Si sheets or bulk alloy, product purity is higher, is tightly combined, and has preferable industrialization prospect.
Description
Technical field
The present invention relates to Ca-Si alloy material systems field, and in particular to a kind of Emission in Cubic Ca3Si alloys and its preparation side
Method.
Background technology
The object being always widely studied from Ca-Si bianry alloys in 1863, the Ca- stablized at normal temperatures and pressures at present
Si bianry alloys have：Ca2Si, Ca5Si3, CaSi, Ca3Si4, Ca14Si19, and CaSi2.However, applying external pressure is
A kind of a kind of effective ways for causing meta-stable or unstable phase in version for stable phase.Test and shown, 10 ~
CaSi under 15GPa pressure3And CaSi6Alloy successfully synthesizes.Due to Ca and Si elements be largely present in nature with
And it is non-toxic, plus the special electronic structure of Ca-Si bianry alloys, so Ca-Si bianry alloys are widely used in each
Field.Such as：Ca2Si and Ca3Si4Possess direct band gap and the semiconductor of indirect band gap respectively, its band gap magnitude is respectively：0.56
EV and 0.34 eV, semi-conducting material uses in thermoelectricity field and field of optoelectronic devices possesses huge prospect.However,
CaSi possesses chromaking boron structure, and chromaking boron structure possesses hydrogen storage ability well, has shown that CaSi possesses hydrogen storage well through research
With release hydrogen function.CaSi2A kind of and superconductor.
Because Ca atoms have very high vapour pressure, therefore Ca atoms are easy to evaporate so as to be unfavorable for from silicon substrate
Ca and Si phase counterdiffusion, form Ca silicide.And the presence of a variety of phases of Ca-Si bianry alloys, Ca atomic depositions serve as a contrast in Si
Ca is grown on bottom3During Si, Ca can be formed simultaneously2Si, Ca5Si3, CaSi, CaSi2Deng the silicide of calcium, therefore in silicon face extension
Grow Ca3Si is extremely difficult.
The content of the invention
It is an object of the invention in view of the shortcomings of the prior art, providing a kind of Emission in Cubic Ca3Si alloys and preparation method thereof.
The preparation manipulation technique is simple, product component is easy to control, obtained Emission in Cubic Ca3Si alloy materials are expected to using can be extensive
Applied to every field.
To achieve the above object, the present invention adopts the following technical scheme that：
A kind of Ca3Si alloys, Ca and Si component molar ratio are 3:1, space group is, lattice constant 4.8336
Å；Si atoms occupy four summits, and Ca atoms are in cubical 6 center of areas；Its preparation method comprises the following steps：
（1）Ca powder and Si powder are pressed 3.0 ~ 3.5:1 mol ratio is well mixed under Ar protective atmospheres, obtains mixture；
（2）By step（1）Gained mixture, by ball grinder good seal, is kept away in Ar gas shielded atmosphere transfers ball grinder
Exempt from oxygen entrance；
（3）By step（2）In ready ball grinder, be put into ball mill and ball carried out with 1000 ~ 2000 rpm rotating speed
30 ~ 80 h are ground, powder is fully reacted, obtains uniform mixed powder；
（4）By step（3）In obtained uniform mixed powder take out, in the stainless steel mould of specification needed for loading, adopt
The mode sintered with vacuum plasma, 100 ~ 500 DEG C are warming up under 50 ~ 600 MPa pressure, keep 10 ~ 120 min to enter
Row vacuum-sintering tabletting, produces Ca3Si sheets or bulk alloy material.
Step（2）Middle ball material mass ratio is：5~20:1.
Step（2）The particle diameter of middle mill ball is 0.2 ~ 1.5 cm, using preceding clear using acetone, alcohol progress ultrasonic wave successively
Wash, ultrasonic wave cleaning total time is 20 ~ 30 min.
Step（4）Middle sintering heating rate is 10 ~ 30 DEG C/min.
The beneficial effects of the present invention are：
1）Cryomilling and plasma discharging vaccum sintering process are combined by the present invention, and technique is simple, and operation is held
Easily, and reaction temperature is relatively low, is less prone to the oxidation reaction and Ca of Ca atoms3The decomposition of Si phases, composition are controllable；
2）Supported the use in sintering process of the present invention as stainless steel mould, higher burning can be born at a lower temperature
Knot pressure power, the oxidation and volatilization of Ca in general sintering process are efficiently controlled, therefore product composition is purer, density is higher, finally
Phase structure is Emission in Cubic Ca3Si。
Brief description of the drawings
Fig. 1 is that XRD corresponding to invention is composed；
Fig. 2 is Ca3Si structural representation；
Fig. 3 is Ca3Si conductivity versus temperature curve；
Fig. 4 is Ca3Si Seebeck coefficient-temperature curve；
Fig. 5 is Ca3Si power factor-temperature curve.
Embodiment
Below in conjunction with specific embodiment, the present invention will be further described, but the present invention is not limited only to these embodiments.
Embodiment 1
A kind of Emission in Cubic Ca3The preparation method of Si alloy materials, comprises the following steps：
（1）Ca powder and Si powder are pressed 3.0:1 mol ratio is well mixed under Ar protective atmospheres, obtains mixture；
（2）By step（1）Gained mixture, mill ball and stainless steel jar mill and electronic balance are put into big filled with one
In air pressure Ar glove box, wherein ball material mass ratio is 5:1 configuration, in glove box after accurate weighing, is put into ball grinder, will
Ball grinder good seal, avoids oxygen from entering, and ball grinder is then taken out from glove box；
（3）By step（2）In ready ball grinder, be put into ball mill and ball milling 30 carried out with 2000 rpm rotating speed
H, powder is set fully to react；
（4）By step（3）In completely reacted powder take out, it is in 10 mm stainless steel moulds, using true to be fitted into diameter of bore
The modes of empty plasma agglomeration, 300 DEG C are warming up under 300 MPa pressure and keeps 120 min to carry out vacuum-sintering tabletting,
Heating rate is 10 DEG C/min, produces Emission in Cubic Ca3Si disc-shaped alloy materials.
Ultrasonic wave cleaning is carried out using acetone, alcohol successively using preceding in stainless-steel vacuum ball grinder, ultrasonic wave cleaning is total
Time is 30 min.
Embodiment 2
A kind of Emission in Cubic Ca3The preparation method of Si alloy materials, comprises the following steps：
（1）Ca powder and Si powder are pressed 3.3:1 mol ratio is well mixed under N protective atmospheres, obtains mixture；
（2）By step（1）Mixture, mill ball and the stainless steel jar mill and electronic balance of gained are put into filled with one
In atmospheric pressure Ar glove box, wherein ball material mass ratio is 16:1 configuration, in glove box after accurate weighing, is put into ball grinder
In, by ball grinder good seal, avoid oxygen from entering, ball grinder is then taken out from glove box；
（3）By step（2）In ready ball grinder, be put into ball mill and ball milling 80 carried out with 1000 rpm rotating speed
H, powder is set fully to react；
（4）By step（3）In completely reacted powder take out, load stainless steel mould of the hollow size for the mm of 12 mm × 6
In, by the way of vacuum plasma sintering, 500 DEG C are warming up under 50 MPa pressure and keeps 20 min to carry out vacuum burning
Knot pressure piece, heating rate are 10 DEG C/min, produce Emission in Cubic Ca3Si bulk alloy materials.
The particle diameter of mill ball is 1.5 cm in stainless-steel vacuum ball grinder, is surpassed successively using acetone, alcohol using preceding
Sound wave cleans, and ultrasonic wave cleaning total time is 20 min.
Embodiment 3
A kind of Emission in Cubic Ca3The preparation method of Si alloy materials, comprises the following steps：
（1）Ca powder and Si powder are pressed 3.5:1 mol ratio is well mixed under He gas shielded atmosphere, obtains mixture；
（2）The mixture, mill ball and stainless steel jar mill and electronic balance are put into filled with an atmospheric pressure Ar
Glove box in, wherein ball material mass ratio be 8:1 configuration, in glove box after accurate weighing, is put into ball grinder, by ball grinder
Good seal, avoid oxygen from entering, ball grinder is then taken out from glove box；
（3）By step（2）In ready stainless-steel vacuum ball grinder, be put into ball mill to enter with 1500 rpm rotating speed
The h of row ball milling 50, makes powder fully react；
（4）By step（3）In completely reacted powder take out, is fitted into the mm stainless steel moulds of hollow 10 mm × 10, use
The modes of vacuum plasma sintering, 100 DEG C are warming up under 600 MPa pressure and keeps 60 min to carry out vacuum-sintering tabletting,
Heating rate is 12 DEG C/min, produces the Emission in Cubic Ca that the length of side is 10mm3Si bulk alloy materials.
Mill ball particle diameter is 1.0 cm in stainless-steel vacuum ball grinder, and ultrasound is carried out using acetone, alcohol successively using preceding
Ripple cleans, and ultrasonic wave cleaning total time is 20 min.
Embodiment 4
A kind of Emission in Cubic Ca3The preparation method of Si alloy materials, comprises the following steps：
（1）Ca powder and Si powder are pressed 3.2:1 mol ratio is well mixed under He gas shielded atmosphere, obtains mixture；
（2）The mixture, mill ball and stainless steel jar mill and electronic balance are put into filled with an atmospheric pressure Ar
Glove box in, wherein ball material mass ratio be 20:1 configuration, in glove box after accurate weighing, is put into ball grinder, by ball milling
Tank good seal, avoids oxygen from entering, and ball grinder is then taken out from glove box；
（3）By step（2）In ready stainless-steel vacuum ball grinder, be put into ball mill to enter with 1600 rpm rotating speed
The h of row ball milling 45, makes powder fully react；
（4）By step（3）In completely reacted powder take out, is fitted into the mm stainless steel moulds of hollow 10 mm × 10, use
The modes of vacuum plasma sintering, 200 DEG C are warming up under 400 MPa pressure and keeps 30 min to carry out vacuum-sintering tabletting,
Heating rate is 20 DEG C/min, produces Emission in Cubic Ca3Si bulk alloy materials.
Mill ball particle diameter is 0.2 cm in stainless-steel vacuum ball grinder, and ultrasound is carried out using acetone, alcohol successively using preceding
Ripple cleans, and ultrasonic wave cleaning total time is 20 min.
Embodiment 5
A kind of Emission in Cubic Ca3The preparation method of Si alloy materials, comprises the following steps：
（1）Ca powder and Si powder are pressed 3.4:1 mol ratio is well mixed under He gas shielded atmosphere, obtains mixture；
（2）The mixture, mill ball and stainless steel jar mill and electronic balance are put into filled with an atmospheric pressure Ar
Glove box in, wherein ball material mass ratio be 12:1 configuration, in glove box after accurate weighing, is put into ball grinder, by ball milling
Tank good seal, avoids oxygen from entering, and ball grinder is then taken out from glove box；
（3）By step（2）In ready stainless-steel vacuum ball grinder, be put into ball mill to enter with 1800 rpm rotating speed
The h of row ball milling 40, makes powder fully react；
（4）By step（3）In completely reacted powder take out, is fitted into the mm stainless steel moulds of hollow 10 mm × 10, use
The modes of vacuum plasma sintering, 400 DEG C are warming up under 500 MPa pressure and keeps 10 min to carry out vacuum-sintering tabletting,
Heating rate is 30 DEG C/min, produces Emission in Cubic Ca3Si bulk alloy materials.
Mill ball particle diameter is 0.5 cm in stainless-steel vacuum ball grinder, and ultrasound is carried out using acetone, alcohol successively using preceding
Ripple cleans, and ultrasonic wave cleaning total time is 25 min.
Fig. 1 is the Ca obtained by the preparation method of the present invention3The XRD spectrum of Si alloy materials, as can be seen from the figure
Ca3Si several diffraction maximums are all very clear, illustrate the method for the present invention and can obtain the Ca of well-crystallized3Si films.
Fig. 2 is the Ca derived from Fig. 1 XRD3Si crystal structure, as can be seen from the figure Ca atoms occupy cubical
Six center of areas, Si atoms occupy cubical eight summits；Table 1 is Ca3The structure of Si alloys, space group are, its lattice
Constant is 4.8336.
Table 1 is Ca3Si atom site
Fig. 3-Fig. 5 is Emission in Cubic Ca produced by the present invention3The related index parameter of the thermoelectricity capability of Si alloy materials is with temperature
The curve map of change is spent, as can be seen from the figure as the increase of temperature, the electrical conductivity of material decline, Seebeck coefficient increases,
Power factor raises, and illustrates there is preferable thermoelectric applications prospect.
The foregoing is only presently preferred embodiments of the present invention, all equivalent changes done according to scope of the present invention patent with
Modification, it should all belong to the covering scope of the present invention.
Claims (5)
- A kind of 1. Emission in Cubic Ca3The preparation method of Si alloys, it is characterised in that：The Ca3The Ca and Si of Si alloys Component molar Than for 3:1, space group is, lattice constant 4.8336, Si atoms occupy four summits, and Ca atoms are in cube 6 center of areas, its preparation method specifically includes following steps：（1）By Ca powder and Si powder in molar ratio 3.0 ~ 3.5:1 is well mixed under Ar protective atmospheres, obtains mixture；（2）By step（1）Gained mixture, by ball grinder good seal, avoids oxygen in Ar gas shielded atmosphere transfers ball grinder Gas enters；（3）By step（2）In ready ball grinder, be put into ball mill with 1000 ~ 2000 rpm rotating speed carry out ball milling 30 ~ 80 h, make powder fully react, and obtain uniform mixed powder；（4）By step（3）In obtained uniform mixed powder take out, in the stainless steel mould of specification needed for loading, using true The mode of empty plasma agglomeration, 100 ~ 500 DEG C are warming up under 50 ~ 600 MPa pressure, keep 10 ~ 120 min to carry out true Sky sintering tabletting, produces Ca3Si sheets or bulk alloy material.
- 2. Emission in Cubic Ca according to claim 13The preparation method of Si alloys, it is characterised in that：Step（2）Middle ball material matter Measuring ratio is：5~20:1.
- 3. Emission in Cubic Ca according to claim 13The preparation method of Si alloys, it is characterised in that：Step（2）Middle mill ball Particle diameter be 0.2 ~ 1.5 cm, using it is preceding successively using acetone, alcohol carry out ultrasonic wave cleaning, ultrasonic wave cleaning total time be 20 ~30 min。
- 4. Emission in Cubic Ca according to claim 13The preparation method of Si alloys, it is characterised in that：Step（4）Middle sintering rises Warm speed is 10 ~ 30 DEG C/min.
- 5. one kind Emission in Cubic Ca made from preparation method as described in claim any one of 1-43Si alloy materials.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101792144A (en) * | 2009-10-28 | 2010-08-04 | 无锡润鹏复合新材料有限公司 | Face-centred cubic structure Ti3Si nano particles and preparation method thereof |
| CN104004935A (en) * | 2014-05-27 | 2014-08-27 | 武汉理工大学 | Method for super-rapidly preparing high-performance high-silicon-manganese thermoelectric material |
| CN105932148A (en) * | 2016-06-22 | 2016-09-07 | 福州大学 | Ag-doped cubic-phase Ca2Si thermoelectric material |
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| JP3584284B2 (en) * | 2001-03-23 | 2004-11-04 | 静岡大学長 | Growth method of calcium silicide thin film |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101792144A (en) * | 2009-10-28 | 2010-08-04 | 无锡润鹏复合新材料有限公司 | Face-centred cubic structure Ti3Si nano particles and preparation method thereof |
| CN104004935A (en) * | 2014-05-27 | 2014-08-27 | 武汉理工大学 | Method for super-rapidly preparing high-performance high-silicon-manganese thermoelectric material |
| CN105932148A (en) * | 2016-06-22 | 2016-09-07 | 福州大学 | Ag-doped cubic-phase Ca2Si thermoelectric material |
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